Block copolymers of polyphenylene oxides and polyformals on non-sterically-hindered dihydric phenols

ABSTRACT

The invention relates to block copolymers of polyphenylene oxides and polyformals of non-sterically-hindered dihydric phenols. These block copolymers can be molded, calendered, or extruded as films, sheets, fibers, laminates or other useful articles of manufacture.

CROSS REFERENCE TO RELATED APPLICATIONS

This invention is related to U.S. patent applications Ser. Nos. 222,409 entitled "Formal-Coupled Polyphenylene Oxides," filed Jan. 5, 1981 of Dwain Montgomery White and George Raymond Loucks, and (220,662) entitled "Block Polymers of Polyphenylene Oxide and Aromatic Polyformals," filed Dec. 29, 1980 of Dwain Montgomery White. Both applications are assigned to the assignee of this invention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to block copolymers of polyphenylene oxides and polyformals of non-sterically-hindered dihydric phenols. These block copolymers can be molded, calendered, or extruded as films, sheets, fibers, laminates or other useful articles of manufacture.

2. Description of the Prior Art

Polyphenylene oxides having an average hydroxyl group per molecule of 1.0 or less are described in A. S. Hay's U.S. Pat. Nos. 3,306,879; 3,914,266; and 4,028,341; among others.

Polyphenylene oxides having an average hydroxyl group per molecule greater than zero including 2.0 or less are described in D. M. White's U.S. Pat. Nos. 4,140,675 and 4,234,706 are among others.

Polyformals are described in R. Barclay, Jr.'s U.S. Pat. No. 3,069,386, A. S. Hay's copending U.S. Ser. No. 858,040, filed Nov. 6, 1978, now U.S. Pat. No. 4,134,734, and G. R. Loucks et al., U.S. Ser. No. 889,397, filed Mar. 23, 1978 now U.S. Pat. No. 4,260,733.

DESCRIPTION OF THE INVENTION

This invention embodies block copolymers of polyphenylene oxides and polyformals of non-sterically-hindered dihydric phenols.

In general, illustrative of the broad group of block polymers of polyphenylene oxides and polyformals of non-sterically-hindered dihydric phenols (hereinafter also referred to as "NSH-dihydric phenols") included within the scope of this invention are those described, among others by the following model structures: ##STR1## wherein x is a number of from 1 to 200 or higher, often preferably from 30 to 100, and frequently from 40 to 70.

The above illustrative linear combinations of mono- and poly-functional polyphenylene oxides, non-sterically-hindered aromatic polyformals including random and/or alternating arrangements of the polymer segments defined by the units A, B, (CZ)_(x), and coupling agent Z, which units and coupling agents are described in greater detail hereafter, are not intended to limit the combinations that can be obtained by the practice of this invention.

The expression polyphenylene oxides includes "monofunctional polyphenylene oxides" well known to those skilled in the art having an average hydroxyl group per molecule value greater than zero including 1.0 or less. These polyphenylene oxides can be prepared by any of the methods of the prior art, and may be illustrated by formula (II) set out hereafter: ##STR2## where independently each R is hydrogen, a hydrocarbon radical, a halohydrocarbon radical, a hydrocarbonoxy radical or a halohydrocarbonoxy radical, m is a number of at least 1, preferably 10, and more preferably 40 to 170. The monofunctional polyphenylene oxide units of the block polymers can be conceptualized by the structure of formula (II) above wherein the hydrogen atom is disassociated from the monohydroxy group of the polyphenylene oxide, i.e., a phenoxy radical, which may be referred to as a monovalent phenoxy radical, abbreviated herein by the formula-A.

The expression "polyphenylene oxide" also includes "polyfunctional polyphenylene oxides" also well known to those skilled in the art including quinone-coupled polyphenylene oxides having an average hydroxyl group per molecule greater than zero including 2.0 or less. These polyphenylene oxides can be prepared by the methods described in U.S. Pat. No. 4,234,706 and may be illustrated by formula (III) set out hereafter: ##STR3## wherein independently --OEO-- is a divalent quinone residue, E is a divalent arene radical, either a or b is at least equal to 1, the sum of a plus b is preferably at least equal to 10, more preferably 40 to 170, and R is the same as in formula (II) above. The polyfunctional polyphenylene oxide units of the block polymers can be conceptualized by the structure of formula (III) above wherein the hydrogen atoms are disassociated from the hydroxy groups of the quinone-coupled polyphenylene oxide, i.e., a quinone-coupled polyphenoxy radical, which may be referred to as a divalent phenoxy radical, abbreviated herein by the formula --B--.

The expression "NSH-dihydric phenols" as employed herein and in the claims includes any dihydric phenol free of steric-hindrance, i.e. dihydric phenols having neither hydroxy group sterically-hindered by the presence of more than one halogen, hydrocarbon or hydrocarbonoxy group ortho-positioned relative to the hydroxy groups of the dihydric phenol. Sterically-hindered as defined herein as the presence of a halogen, hydrocarbon or hydrocarbonoxy group directly bonded to each carbon atom ortho-positioned (adjacent to) the carbon atoms directly bonded to the hydroxyl groups of the dihydric phenol. These dihydric phenols are well known to those skilled in the art and can be illustrated by formula (IV) set out hereafter: ##STR4## where R_(f) is an alkylene, alkylidene including "vinylidene," cycloalkylene, cycloalkylidene or arylene linkage or a mixture thereof, a linkage selected from the group consisting of ether, carbonyl, amine, a sulfur or phosphorous containing linkage, Ar and Ar' are arene radicals, Y is bromine, chlorine or a monovalent alkyl or alkoxy group, each d represents a whole number up to a maximum equivalent to the number of replaceable hydrogens substituted on the aromatic rings comprising Ar or Ar'--subject to the proviso that when d is equal to 2 or more, no more than one Y group is ortho-positioned relative to an --OH group, X is bromine, chlorine or a monovalent hydrocarbon group selected from the class consisting of alkyl, aryl and cycloalkyl including mixtures thereof, e represents a whole number of from 0 to a maximum controlled by the number of replaceable hydrogens on R_(f), aa, bb and cc represent whole numbers including 0, when bb is not zero, neither aa or cc may be zero, otherwise either aa or cc but not both may be 0, when bb is zero, the aromatic groups can be joined by a direct carbon bond.

Included in the NSH-dihydric phenols of formula (IV) are, for example, the following:

resorcinol;

4,4'-dihydroxy-diphenyl;

1,6-dihydroxy-naphthalene;

2,6-dihydroxy-naphthalene;

4,4'-dihydroxy-diphenyl methane;

4,4'-dihydroxy-diphenyl-1,1-ethane;

4,4'-dihydroxy-diphenyl-1,1-butane;

4,4'-dihydroxy-diphenyl-1,1-isobutane;

4,4'-dihydroxy-diphenyl-1,1-cyclopentane;

4,4'-dihydroxy-diphenyl-1,1-cyclohexane;

4,4'-dihydroxy-diphenyl-phenyl methane;

4,4'-dihydroxy-diphenyl-2-chlorophenyl methane;

4,4'-dihydroxy-diphenyl-2,4-dichlorophenyl methane;

4,4'-dihydroxy-diphenyl-p-isopropylphenyl methane;

4,4'-dihydroxy-diphenyl-2,2-propane;

4,4'-dihydroxy-3-methyl-diphenyl-2,2-propane;

4,4'-dihydroxy-3-cyclohexyl-diphenyl-2,2-propane;

4,4'-dihydroxy-3-methoxy-diphenyl-2,2-propane;

4,4'-dihydroxy-3,3'-dimethyl-diphenyl-2,2-propane;

4,4'-dihydroxy-3,3'-dichloro-diphenyl-2,2-propane;

4,4-dihydroxy-diphenyl-2,2-butane;

4,4'-dihydroxy-diphenyl-2,2-pentane;

4,4'-dihydroxy-diphenyl-2,2-(4-methyl pentane);

4,4'-dihydroxy-diphenyl-2,2-n-hexane;

4,4'-dihydroxy-diphenyl-2,2-nonane;

4,4'-dihydroxy-diphenyl-4,4-heptane;

4,4'-dihydroxy-diphenyl phenylmethyl methane;

4,4'-dihydroxy-4-chlorophenylmethyl methane;

4,4'-dihydroxy-diphenyl-2,5-dichlorophenylmethyl methane;

4,4'-dihydroxy-diphenyl-3,4-dichlorophenylmethyl methane;

4,4'-dihydroxy-diphenyl-2-napthylmethyl methane;

4,4'-dihydroxy-tetraphenyl methane;

4,4'-dihydroxy-diphenyl-1,2-ethane;

4,4'-dihydroxy-diphenyl-1,10-n-decane;

4,4'-dihydroxy-diphenyl-1,6(1,6-dioxo-n-hexane);

4,4'-dihydroxy-diphenyl-1,10(1,10-dioxo-n-decane);

bis-p-hydroxy-phenylether-4,4'-biphenyl;

a,a,a',a'-tetramethyl-a,a'-(di-p-hydroxyphenyl)-p-xylene;

a,a,a',a'-tetramethyl-a,a'-(di-p-hydroxyphenyl)-m-xylylene;

4,4'-dihydroxy-3,3'-dimethyl-diphenyl methane;

4,4'-dihydroxy-2,2'-dimethyl-diphenyl methane;

4,4'-dihydroxy-3,3'-dichloro-diphenyl methane;

4,4-dihydroxy-3,3'-dimethoxy-diphenyl methane;

4,4'-dihydroxy-2,2',5,5'-tetramethyl-diphenyl methane;

4,4'-dihydroxy-2,2'-dimethyl-5,5'-diisopropyldiphenyl methane;

4,4'-dihydroxy-2,2',-dimethyl-5,5'-dipropyl-diphenyl methane;

4,4'-dihydroxy-2,2'-dimethyl-5,5'-di-tert.-butyldiphenyl methane;

4,4'-dihydroxy-diphenyl-5,5-nonane;

4,4'-dihydroxy-diphenyl-6,6-undecane;

4,4'-dihydroxy-diphenyl-3,3-butanone-2;

4,4'-dihydroxy-diphenyl-4,4-hexanone-3;

4,4'-dihydroxy-diphenylmethyl-4-methoxyphenyl methane;

4,4'-dihydroxy-diphenyl ether;

4,4'-dihydroxy-diphenyl sulfide;

4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

4,4'-dihydroxy-diphenyl sulfoxide;

4,4'-dihydroxy-diphenyl sulfone;

4,4'-dihydroxy-3,3'-dichlorodiphenyl sulfone;

2,2'-bis (4-hydroxyphenyl)-1-chloroethylene;

2,2'-bis (4-hydroxyphenyl)-1,1-dichloroethylene; and

2,2-bis (4-hydroxyphenyl)-1,1-dibromoethylene; etc.

The difunctional non-sterically-hindered dihydric phenol portion of the polymers can be conceptualized by the structure of formula (IV) above wherein the hydrogen atoms are disassociated from the hydroxyl groups of the NSH-dihydric phenols, and is abbreviated herein by the formula --C--.

The expression "methylene halides" as employed herein and in the claims includes dichloromethane which is more commonly known as methylene chloride, dibromomethane, bromochloromethane including mixtures thereof. The coupling agent of the block copolymers can be conceptualized by the --CH₂ -- divalent methylene radical wherein the halogen atoms are disassociated from the methylene halides. These radicals are abbreviated herein by the symbol --Z--.

The "polyformals of non-sterically-hindered dihydric phenols" (hereinafter also referred to as "NSH-aromatic polyformals") are formed "in situ" in accordance with the process described herein. The NSH-aromatic polyformal segments associated with the block copolymers may be illustrated by formula (V) set out hereafter: ##STR5## wherein R_(f), Ar, Ar', Y, d, X, e, aa, bb, and cc are as defined above, and are referred to herein as divalent NSH-aromatic polyformal radicals, abbreviated herein by the formula --CZ--_(x) wherein C, Z are as previously defined, and x is a number at least equal to 1.

Presently preferred NSH-aromatic-PF units may be illustrated by formulas (VI) and (VII) set out hereafter: ##STR6## wherein R' is hydrogen, bromine, chlorine, or a C₁₋₄ alkyl or alkoxy group, R_(g) and R_(n) are hydrogen or a C₁₋₂ alkyl group, and Z_(a) is hydrogen, chlorine or bromine, subject to the proviso that at least one Z_(a) is chlorine or bromine, and x is as previously defined.

The process of preparing the block copolymers of polyphenylene oxides and polyformals of non-sterically-hindered dihydric phenols requires the combination of the reactants in accordance with the following process sequence:

(1) Reacting a non-sterically-hindered dihydric phenol with methylene halide in the presence of a solvent and a base, and optionally, preferably, a phase transfer agent to form a non-sterically-hindered aromatic polyformal "block,"

(2) adding a homogeneous solution of a polyphenylene oxide in an inert solvent to the resulting NSH-aromatic polyformal solution plus an additional amount of a base, and optionally a phase transfer agent,

(3) reacting the polyphenylene oxide with the aromatic polyformal, and

(4) recovering a block copolymer of polyphenylene oxide and a non-sterically-hindered aromatic polyformal.

The solvents that may be employed include solvents which are generally suitable for preparation of homogeneous solutions of polyphenylene oxide and include medium polar solvents such as chlorobenzene, anisole, bromobenzene, ortho-dichlorobenzene, iodobenzene, acetophenone, N-methylformamide, N,N-dimethylformamide, acetonitrile, nitrobenzene, gamma-butyrolactone, nitromethane, dimethylsulfoxide, sulpholane, N-methylpyrrolidone, etc. and mixtures thereof. Preferably the solvents employed are polar aprotic solvents i.e. solvents substantially incapable of forming strong hydrogen bonds with the hydric groups associated with the polyphenylene oxide reactant or the non-sterically-hindered dihydric phenols during the course of the process reactions. Accordingly, any solvent can be employed which does not deleteriously inhibit the reaction of this process via hydrogen bonding associated with protic organic solvents.

In general, the process can be carried out in any strongly basic reaction medium, preferably, that provided by the presence of a strong inorganic base, including mixtures thereof. Representative of basic species which can be employed are alkali metal hydroxides. Specific examples of the aforementioned are lithium, sodium, and potassium hydroxides; etc. Especially preferred bases are substantially anhydrous sodium hydroxide pellets, e.g., electrolytic grade sodium hydroxide pellets containing at least about 98% NaOH by weight.

Optionally, a catalytic phase transfer agent can be employed to enhance the process reaction rate. Preferably, the phase transfer agents are selected from the group consisting of quaternary ammonium, quaternary phosphonium, and tertiary sulfonium compounds including mixtures thereof. These phase transfer agents are well known and include illustratively "onium compounds" described by C. M. Starks in J.A.C.S. 93, 195 (1971), "crown ethers" described in Aldrichimica ACTA 9, Issue #1 (1976) Crown Ether Chemistry-Principles and Applications, G. W. Gokel and H. D. Durst, as well as C. J. Pederson in U.S. Pat. No. 3,622,577 and "chelated cationic salts" which include alkali or alkaline earth metal diamine halides. Specific illustrative examples are described in U.S. Pat. No. 4,201,721 whose descriptions are incorporated herein in their entirety by reference.

Any amount of a functionally reactive polyphylene oxide, non-sterically-hindered, dihydric phenol and methylene halide can be employed, subject to the proviso that the methylene halide be present in stoichiometric amounts at least sufficient to react with the hydroxy groups associated with the polyphenylene oxide and the NSH-dihydric phenols. Preferably the methylene halide is present in excess of from about 1.25 to as much as 5 to 20 times the stoichiometric amounts required to completely couple all of the polyphenylene oxide and NSH-dihydric phenol reactants.

Any amount of base can be employed. Generally effective mole proportions of base relative to the hydroxyl groups associated with the polyphenylene oxide and the NSH-dihydric phenols are within the range from about 1:1 to 50:1 and frequently preferably are from about 1.1:1.0 to 3:1.

Any amount of the optional phase transfer agent can be employed, however, generally effective mole proportions of phase transfer agent relative to base are within the range of from about 1:10 to about 1:1000 and more frequently preferably are within the range of from about 1:100 to 1:500.

In general, the reactions can be carried out at any temperature. Preferably, temperatures within the range of from about 0° to 150° C. or even higher and more preferably from 50° C. to 100° C. are employed.

The best mode of practicing this invention is set out in Examples hereinafter.

EXAMPLE 1 (A) Preparation of Mono-Functional Polyphenylene Oxide

2.5 gallon stainless steel reactor equipped with an air-driven paddle stirrer, oxygen inlet tube, and water-cooled coil and jacket was charged with 2.3 l toluene, 150 g. 2,6-xylenol, 4.2 ml. of a stock catalyst solution (19.31 g. cuprous oxide added slowly with stirring to 100 ml. of a 47.2% aqueous hydrogen bromide (HBr) solution), 3.4 g. N,N'-di(t-butyl)ethylene diamine (DBEDA), 47.5 g. N,N-dimethylbutylamine (DMBA), 1.5 g. di(n-butyl)amine (DBA) and 1.5 g. tricaprylylmonomethylammonium chloride (Adogen 464). Oxygen was bubbled into the resulting admixture at a rate of 8.3 moles per hour while vigorously agitating the admixture, and 1350 g. of 2,6-xylenol dissolved in 1.5 l of toluene was pumped into the reactor over a 30 minute period. The temperature rose from 25° to 35° C. The polymerization reaction was terminated by replacing the oxygen stream with nitrogen and adding 15 ml. of a 38% aqueous solution of trisodium ethylenediamine tetraacetate (Na₃ EDTA). The resulting reaction mixture was heated at 50°-55° C. under nitrogen for about one hour and the polymer was precipitated by adding three volumes of methanol. The precipitated polymer was filtered and washed with methanol yielding a white solid polymeric product having an intrinsic viscosity of 0.24 dl./g. measured in chloroform at 25° C. From the infrared absorption at 3610 cm⁻¹ an average hydroxyl content of 1.1 --OH groups per polymer chain was calculated. Molecular weight determination by GPC analysis based on a polystyrene calibration furnished the following data:

    ______________________________________                                         --Mw            =     17,260                                                   --Mn            =     8,800                                                    --Mw/--Mn       =     1.96                                                     ______________________________________                                    

(B) Preparation of Poly-Functional Polyphenylene Oxide

A 500 ml. 3-neck round-bottom flask equipped with condenser, N₂ "bubbler" and mechanical stirrer was charged with 50.0 g. of mono-functional polyphenylene oxide--prepared as described in (A) above, 1.72 g. TMDQ (tetramethyl diphenoquinone) and 200 ml. of toluene. The mixture was heated under N₂ at 65°-70° C. for 3.5 hours. The solution was diluted with 150 ml. of toluene and transferred to a 1 quart Waring blender. With vigorous agitation, the polymer was coagulated by addition of 1 liter of methanol. The light yellow product was twice reslurried in methanol, then collected and dried in vacuo at ˜50° C. overnight. The polymer had an intrinsic viscosity of 0.28 dl./g. measured in chloroform at 25° C. From the infrared absorption at 3610 cm⁻¹ an average hydroxyl content of 1.8 --OH groups per polymer chain was calculated. Molecular weight determination by GPC analysis based on a polystyrene calibration furnished the following data:

    ______________________________________                                          -- Mw          =     23,890                                                    --Mn           =      8,560                                                   -- Mw/ -- Mn    =     2.79                                                     ______________________________________                                    

EXAMPLE 2 (A) Preparation of Block Copolymers of Polyphenylene Oxides and Polyformals of Non-Sterically-Hindered Dihydric Phenols

A series of block copolymers was prepared according to the following process sequence:

(1) Reacting a non-sterically-hindered dihydric phenol with methylene halide in the presence of a solvent, e.g., N-methylpyrrolidone, and a base, e.g., sodium hydroxide pellets to from a polyformal block,

(2) Adding to this a polyphenylene oxide prepared as described in EXAMPLE 1 (A) or (B), in solution in an inert solvent, e.g., chlorobenzene, and additional base,

(3) Reacting the polyphenylene oxide with the aromatic polyformal, and

(4) Recovering a block copolymer of a polyphenylene oxide and a non-sterically-hindered aromatic polyformal.

A detailed procedure with respect to Run No. I, further described in Tables I and II, follows.

A 500 ml. flask equipped with a mechanical stirrer, thermometer and condenser having a nitrogen bubbler attached was flushed with nitrogen and charged with 24.3 g. of 4,4'-dihydroxy-diphenyl-2,2-propane also known as bis(4-hydroxyphenyl)propane-2,2, i.e., bisphenol-A, 60 mls. of N-methylpyrrolidone, and 40 ml. of methylene chloride. The mixture was stirred at room temperature until the bisphenol-A was completely dissolved. The flask was heated and maintained at about 70° C. in a constant temperature bath. 8.53 g. (98% of stoichiometric weight) of sodium hydroxide pellets (electrolytic grade) was added. After stirring at reflux for 160 minutes a low molecular weight aromatic BPA polyformal block was formed having an intrinsic viscosity of 0.17 dl./g. when measured in CHCl₃ at 25° C. A solution of 8.2 g. of monofunctional polyphenylene oxide prepared as in EXAMPLE I (A) above--in 25 ml. of monochlorobenzene, and 2.84 g. of sodium hydroxide pellets--again electrolytic grade, i.e., 98% were added. After the resulting reaction mixture was stirred at about 70° C. for 80 minutes, the resulting block copolymer solution was diluted with 300 ml. of chlorobenzene and transferred to a high speed mixing blender. The block copolymer was coagulated by the addition of a methanol/acetone mixture--containing equal parts by volume of each, during continuous agitation under high speed mixing conditions. The resulting admixture was reslurried in ˜1.0 liter of water to remove residual sodium chloride, washed with ˜1.0 liter of methanol and dried in vacuo at about 50° C. 27.3 g. of block copolymer having an intrinsic viscosity of 1.32 dl./g. measured in chloroform at 25° C. was isolated. By proton nmr analysis the block copolymer was formed to contain 28 wt. % polyphenylene oxide.

A sample of the resulting block copolymer was compression molded into disks 1 mm. thick and 2.5 cm. in diameter at 270° C. and 5000 psi in a laboratory press. The disks were transparent indicating a single phase solid solution.

A resume of the product reaction parameters and product properties are set out in Tables I and II, respectively, which correspond to a series of runs carried out in a manner analogous to that described in detail above.

                                      TABLE I                                      __________________________________________________________________________     REACTION PARAMETERS                                                            Run                                                                               BPA                                                                               PF    PPO                                                                               PPO                                                                               NaOH NMP  φCl                                                                           CH.sub.2 Cl.sub.2                               No.                                                                               (g)                                                                               [η]                                                                              (g)                                                                               [η]                                                                           (g)  (ml) (ml)                                                                              (ml)                                            __________________________________________________________________________     I  24.3                                                                              0.17  8.2                                                                               0.24                                                                              11.37                                                                               60   25 40                                                          (A)                                                                II 24.3                                                                              0.11  25.6                                                                              0.24                                                                              11.37                                                                               60   50 40                                                          (A)                                                                III                                                                               5.2                                                                                0.10-                                                                               17.3                                                                              0.24                                                                              2.52 45   25 30                                                    0.15  (A)                                                                IV 24.3                                                                              ˜0.15                                                                          8.2                                                                               0.28                                                                              11.1 60   25 40                                                          (B)                                                                __________________________________________________________________________

                  TABLE II                                                         ______________________________________                                         COPOLYMER PROPERTIES                                                                                    Wt.                                                   Run  Yield               %    GPC Data                                         No.  (g)     [η]                                                                               T.sub.g                                                                               PPO  --Mw  --Mn  --Mw/--Mn                          ______________________________________                                         I    27.3    1.32    97° C.                                                                        28   189,000                                                                              24,860                                                                               7.6                                II   50.0    0.73   99° C. &                                                                       54   90,000                                                                               37,530                                                                               2.4                                                    169° C.                                             III  20.9    0.60   188° C.                                                                        77   62,240                                                                               28,130                                                                               2.2                                IV   30.5    0.55   --     24   70,540                                                                               20,130                                                                               3.5                                ______________________________________                                    

In general, the formal-coupled polyphenylene oxide and non-sterically-hindered dihydric phenols based upon the observed T_(g) values (T_(g) values determined employing differential scanning procedure (DSC) techniques in accordance with the teachings set out in J. Chiu, Polymer Characterization by Thermal Methods of Analysis, New York, Marcel Dekker, Inc. (1974)) depending on the relative amounts of polyphenylene oxide and NSH-aromatic polyformal block segments contained by the copolymers exhibit (1) a single phase solid solution, i.e., block copolymers exhibiting complete compatibility or (2) multiple phase solid solutions, i.e. block copolymers exhibiting only partial compatibility. In general the relative proportions on a weight percent basis of polyphenylene oxide and non-sterically-hindered aromatic polyformal blocks corresponding to single or multiple phase solid solutions are within the ranges set out below in Table III.

                  TABLE III                                                        ______________________________________                                         PPO       NSH-APF                                                              (wt. %)   (wt. %)         Solid Solution                                       ______________________________________                                          1-35     99-65           Single Phase                                         35-65     65-35           Multiple Phase                                       99-65      1-35           Single Phase                                         ______________________________________                                    

In general, the block copolymers of this invention, preferably exhibit intrinsic viscosities greater than about 0.30 and more preferably greater than about 0.45 deciliters per gram measured in chloroform at 25° C.

The formal-coupled block polymers of this invention can be molded, calendered, or extruded as films, sheets, fibers, laminates or other useful articles of manufacture at temperatures of about 300° F. to about 550° F. employing conventional processing equipment for engineering thermoplastic materials including extruders, e.g. mono and multiple screw types, mills or other mechanical equipment which subject engineering thermoplastic materials to high sheer stress at elevated temperatures. 

I claim:
 1. A block copolymer of polyphenylene oxide and polyformals of a non-sterically-hindered dihydric phenol.
 2. A block copolymer of a polyphenylene oxide and polyformals of a non-sterically-hindered dihydric phenol comprising:(i) a polyphenylene oxide radical of the formulas: ##STR7## wherein independently each R is a hydrogen, a hydrocarbon radical, a halohydrocarbon radical, a hydrocarbonoxy radical or halohydrocarbonoxy radical, m is a number of at least 1, or ##STR8## wherein independently the --OEO-- is a divalent quinone residue, E is a divalent arene radical, either a or b is at least equal to 1 and the sum of a plus b is at least equal to 10, R is the same as above, and (ii) a non-sterically-hindered aromatic polyformal radical of the formula ##STR9## wherein R_(f) is alkylene including "vinylidene," alkylidene, cycloalkylene, cycloalkylidene or arylene linkage or a mixture thereof, a linkage selected from the group consisting of ether, carbonyl, amine, a sulfur or phosphorous containing linkage, Ar and Ar' are arene radicals, Y is bromine, chlorine or a monovalent alkyl or alkoxy group, each d represents a whole number up to a maximum equivalent to the number of replaceable hydrogens substituted on the aromatic rings comprising Ar or Ar'--subject to the proviso that when d is equal to 2 or more, no more than one Y group is ortho-positioned relative to an --OH group, X is bromine, chlorine or a monovalent hydrocarbon group selected from the class consisting of alkyl, aryl and cycloalkyl and mixtures thereof, e represents a whole number of from 0 to a maximum controlled by the number of replaceable hydrogens on R_(f), aa, bb and cc represent whole numbers including 0, when bb is not zero, neither aa nor cc may be zero, otherwise either aa or cc but not both may be 0, when bb is zero, the aromatic groups can be joined by a direct carbon bond, x is a number of at least 1, and (iii) a methylene radical of the formula --CH₂ --.
 3. The claim 2 polymer wherein the non-sterically-hindered aromatic polyformal radical is of the formulas: ##STR10## where independently each R¹ is hydrogen, bromine, chlorine, or a C₁₋₄ alkyl or alkoxy group, R_(g) and R_(h) are hydrogen or a C₁₋₂ monovalent alkyl group, and each Z_(a) is hydrogen, chlorine or bromine, subject to the proviso that at least one Z_(a) is chlorine or bromine, and x is as previously defined.
 4. The claim 3 polymer wherein m is 40 to 170, the sum of a plus b is 40 to 170, and x is 30 to
 200. 5. A process of forming a block copolymer of a polyphenylene oxide and a polyformal of non-sterically-hindered dihydric phenol comprising the following process sequence:(1) reacting a non-sterically-hindered dihydric phenol with a methylene halide in the presence of a solvent, a phase transfer agent, and a base to form a non-sterically-hindered aromatic polyformal block, (2) reacting a polyphenylene oxide and the aromatic polyformal in solution in the presence of a methylene halide and a base, (3) reacting the polyphenylene oxide with the non-sterically-hindered aromatic polyformal, and (4) recovering a block copolymer of a polyphenylene oxide and a non-sterically-hindered aromatic polyformal. 